Process for hydrogen treatment of hydrocarbons



July 30, 1957 w. A. HoRNE ET AL 2,801,208

PROCESS FOR HYDROGENFREATMFNT oF HYDROCARBONS Filed Feb. 4. 1954 HO wie .52..

PRGCESS FOR HYDROGEN 'TREATMENT 0F HYDROCARBONS William A. Horne and Charles W. Montgomery, Oakmont, Pa., assignors to Gulf Research & Development Company, Pittsburgh, Pa., a corporation of Delaware Application February 4, 1954, Serial No. 408,128

7 Claims. (Cl. 196-53) This invention relates to improved procedure for converting a crude petroleum which contains sulfur into products having higher value.

The utilization of crudes which contain substantial amounts of sulfur gives rise to many problems. The cost of any desuufurization process applied to such a crude, or portions thereof, must be balanced against the value of the products produced. The desulfurization of whole crude has been heretofore proposed. However, the value of the desulfurized products thus produced does not in many cases justify the cost of the large capacity high pressure equipment necessary for such complete desulfurization. It is also known to fractionate the crude and to desulfurize certain of the fractions individually. This mode of operation necessitates discarding or uneconomical use of the low grade residual portions which are not ordinarily desulfurized.

This invention has for its object to provide improved procedure for treating a sulfur containing crude whereby the overall utilization of the components of the crude is improved. Another object is to provide an eilicient and economical process for utilizing a sulfur containing crude wherein the heavier portions of the crude are elliciently desulfurized. Another object is to provide improved procedure and an improved catalyst for desulfurizing and hydrocracking particular portions of the crude. Another object is to improve the state of the art.

These and other objects are accomplished by our invention which in its broader aspects includes fractionation of the crude petroleum which contains sulfur to separate a bottoms portion representing between about l percent and 50 percent of the original crude. This bottoms portion is subjected to hydrodesulfurization by contacting with hydrogen at a temperature between about 775 and 880 F. at a pressure between about 200 and 2,000 p. s. i. g. while in the presence of a hydrogenation catalyst. The catalyst is regenerated when suicient coke has been deposited to necessitate regeneration. Under these conditions a high yield of good quality catalytic cracking stock and other desulfurized products are obtained in the most economical manner.

Our invention also includes certain specific modifications of the foregoing, i. 4e., fractionation of the crude petroleum is conducted so as to separate a virgin gasoil fraction (boiling point between about 670-1030 F.)

ited States Patent a A 2,801,208 IC- Patented July 30 1957 and a bottoms portion representing between about 10 and percent of the crude. The virgin gas-oil fraction is catalytically cracked and the products therefrom distilled to obtain a cycle stock or furnace oil boiling between about 400 F. and 670 F. At least part of this cycle stock (preferably all) and the rst mentioned bottoms portion are combined and subjected to hydrodesulfurization by contacting with hydrogen at a temperature between about 775 and 880 F. at a pressure between about 200 and 2,000 p. s. i. g. while in the presence of a hydrogenation catalyst. When required, the catalyst is regenerated by combustion and is re-used in the process.

Our invention also includes carrying out any of the foregoing operations in the presence of a nickel oxidetungsten oxide catalyst and/or under optimum or intermediate severity conditions as will be explained in more detail hereinafter.

In the following examples and description, we have set forth several of the preferred embodiments of our invention but it is to be understood that they are given by way of illustration and not in limitation thereof.

Our invention in all of its forms involves hydrodesulfunzation-hydrocracking of a 1050 percent bottoms either alone or mixed with another hydrocarbon. Therefore the combined hydrodesulfurization and hydrocracking step will first be discussed in detail since it is common to all of the modifications of our invention. This step can be accomplished by means of any hydrogenation catalyst such as metals, oxides and sullides of groups VI and VIII metal elements of the periodic table for instance molybdenum suliide or oxide, nickel, nickel oxide, tungsten oxide, etc., or mixtures of these metals, oxides and sulfides. We have found that a nickel oxide-tungsten oxide catalyst is unusually effective in this particular application in that it gives both a high degree of desulfurization and a high degree of hydrocracking resulting in high yields of lower boiling products of greater value, such as gasoline, fuel oil, etc. This catalyst also has an unexpectedly long life under the repeated regenerations encountered in the process of our invention. The catalyst is preferably deposited on a carrier such as alumina, activated alumina, silica-alumina (such as a cracking catalyst), alumina stabilized with small amounts of silica, etc. Activated alumina stabilized with a small amount of silica is especially effective when employed in combination with the nickel oxide-tungsten oxide cata- ,lyst since it results in further increase in activity and improved life. Approximately 1 to 4 percent silica content is preferred. However the nickel oxide-tungsten oxide catalyst has superior activity and life when used on other carriers.

These catalysts are prepared in known manner. In preparing the preferred nickel oxide-tungsten oxide catalyst it is recommended that the method disclosed in eopending application Serial No. 222,521, filed April 23, 1951, McKinley and Pardee (now Patent No. 2,703,789, March 8, 1955), be used. This application describes pre- .paring an ammonium tungstate solution, adding a nickel nitrate solution thereto and mixing the two solutions in 2,801,208, f' Y m proportions calculated -to --give the desired ratio of oxides. The impregnated carrier is then drained and calcined in the usual manner to convert the impregnant into nickel oxide-tungsten oxide. While we prefer to employ this method of deposition or impregnation since it gives deposition of the oxides in predetermined ratios, other known methods for preparing mixed oxide catalysts may bc used. The use of a nickel oxide-tungsten oxide catalyst containing between about 0.1:1.0 and 2.0:l.0 mol ratio of nickel oxide to tungsten oxide gives maximum rate of hydrogenation and a product having minimum specific gravity and carbon residue, in addition to high desulfurization and hydrocracking. Therefore, we prefer to employ a catalyst within this composition range.

The.cor,r'1bine d `hydrodesulfurizationehydrocracking .op- ,eration may be-carried out `using, a Yftlxed bed i of catalyst .in which -case `the catalyst would .be 1pelleted, lor like .form,and held in the reactorrby supportsfinknowniman yner. On the Vother hand, the .catalyst `may ibe .in Apow- .dered form and used `in ,a ;uidized condition. .LI'nasuch event, :it `,would ,be desirable kto :avoid ,introducing the .liquidportion `of the charged hydrocarbon `ontothe1cata lyst ata fasterrate thanitishydrocracked -oi :the catalyst, otherwise fthejcatalystparticles will become wetted and agglomerated .fa-nd `fluidization @will :be :harmfully af- `fected. fOurgpreferred lmode ofnoperation is Lto introduce the hydrocarbon charge into a reactor containing a xed bed fof catalyst so-that the liquid portion can-'.ow'idown- -wardlyover thecatalyst. This downowingliquidiseffectively hydrocrackejd.anddesulfurized .and at the esame time, the `unconverted portion of the liquid'tendsto Lwash the catalyst and, at least partially, helps inJkeeping the catalystfree of deposits. I .Eventually -coke or carbon is deposited on the catalyst 1n suiicient 4amount to ,cause a decreaselin activity .and necessitate regeneration. The length of .time operation may'continue -beforeregeneration is ynecessary willdepend upon the-temperature employed, thenatureof the charge and the pressure, i. e., lowering the pressure increases coke deposition, as does increasing the temperature. 'Before the coke deposit reaches about twenty percent by weight of the catalyst, the onstream period should be terminated'and the catalyst regenerated. We have yfound that :a throughput of between about 1.0'and Y24 .volumes of charge-.per volume .of catalyst may be used. A ,throughput Vof, about A2 .to 6 is generally .1 most lsatisfactory. However, 'this varies :depending 4upon other con- .-ditions such ,as the specific space velocity, temperature frand,pressure used.

.Whenlthe catalyst has lacquired a 'deposit `ofzcokelwhich .is large `enough to ,require regeneration, the onstream yportionofrthe operation is ,terminated landlthe catalyst .1s .regenerated by combustion to burn-olf thelcoke -deposits. lIngeneralfa temperature of .about 10009-1200 Vshould `be used during this combustion. It -is desir- Iable -to maintain :theitemperature during Yregenerationas `low as lpossible ,to avoid harmfully aifectingthecatalyst. .However, we have found that our catalyst is very-resist- =ant to loss ofactivity even after many regenerationsin 4thepresence of ysteam. It is preferable :to utilize rtwo .ormore-reactorsxand switch the charge toa second re- '.actor during regeneration of the contaminated catalyst.

pressures requiremore expensiveequipmentand involve considerable operating problems, we prefer to operate at .as low la .pressureas possible, such as between about .200.and V1,000 pis. i. Vg. The'hy'drogen isintroduced into the reactor under the pressure selected in a ratio-of between about l-500 and 20,000 cubic `feet of hydrogen per barrello'f reduced crude.

A liquid space velocityofbetween about 0.3 and 2.0 (vol. of oil per hour per vol. of cat.) is generally employed.

We have found that the combined hydrodesulfurization-hydrocracking operation and the overall economy of the process can be improved by fractionating the crude to obtain a heavy gas-oil fraction (distillation range about 670-1030 F.) and an undistilled residue (which with most crudes will vary between about l0 and 50 percent of the crude, i. e., the larger value will be used with lower A. P. I. gravity crudes and the lower value with higher gravity crudes). This gas-oil fraction is then subjected to catalytic cracking and the products distilled to obtain a catalytic gas-oil ordinarily known as light cycle stock boiling between about 400 F. and 670 F. This catalytic cracking is carried out in vvknown manner and does not constitute a part of our invention. This light cycle stock is then combined with the 10 to 50 percent bottoms and the mixture hydrodesulfurizeduand hydrocracked. It has been found that the sulfur inthe catalytic charge stock tends to concentrate in the'light cycle stock so that it is not a satisfactory furnace oil. However, it is desulfurized without substantial cracking into lower boiling products during the desulfurization-hydrocracking operation.

It is advantageous, but not necessary, to pre-fractionate the sulfur containing crude in a two fstep fractionating operation, the first fractionation being at atmospheric pressure. In this-first distillation, -adistillate is removed comprising the lighter portions, including light gas-oil. The bottoms from this distillation is then distilled in a vacuum towertto give a`.disti1llate :having a .corrected rend pointroffabout `10.30 rF. Thisdi'stillate which is a cracking charge stock comprising heavy :gas-oil (distillation rangerabout-670l030.) is removed and abottoms por- 'Ytion is separated constituting components fboiling above 11030" F. :The heavy gas-oil from the vacuum still is `catalytically cracked as mentioned and thelproducts from the catalytic cracking operationlare fractionated and the lightcycle stock separated.

-Wehave-alsofound that it is advantageous torfractionuate'the hydrodesulfurized product `to separate ya heavy vgas-oil fraction boiling at about 670-l030 F. and to sub- :ject this fraction `to catalytic cracking either with the virgin gas-oil fraction or ina separate cracking operation.

=.In--the accompanying drawing we'have illustrated dia- `rgr'ammatically one of the preferred embodiments .of our invention. Referring to the drawing, numeral 2 ,designates an atmospheric distillation unit, numeral 4.a vacuumdistillation unit, numeral 6 a catalyticcrackingunit, numeral 8 an atmospheric :distillation unit, numeral 10 a .hydrodesulfurizationrand hydrocracking unit, and numeral ,12'an atmospheric distillation unit. In carrying `out Vthe .process of Vour invention the crude petroleum to be treated .is fintroducedinto atmospheric distillation unit 2 and dis- -tilled therein toremove yproducts boiling below about 670 F..as1overhea`d or sidestreams. These overhead or sidestream products would include-virgin gasoline, kero- .sene, light gas-oil, etc. The bottoms from unit 2 boiling Vabove about-670 F. are withdrawn and introduced into -vacuum ydistillation Vunit 4 which is at a pressure between labout l0 and 50 mm. and in which an inert carrier gas such as -steam may be used to assist the distillation. The overhead obtained in vacuum distillation unit 4'is a-virgin heavy gas-oil having a boiling range of between about 67.0-l030" F. (corrected to atmospheric pressure). The bottoms fraction from vacuum distillation unit 4 comprisesabout l0 to 50 percent of the original crude charged to atmospheric tower 2. This bottoms is removed and is treated in a manner tobe described below.

-The virgin heavygas-oil overhead from tower 4 is preferably combined with desulfurized heavygas-oil from atmospheric distillation unit .12 and is subjected lto a catalytic cracking operation in unit 6. The products from catalytic. cracking unit 6 then are distilled inatmospheric distillation unit 8, and the catalyticallycrackedmaterials of' low boiling point such aslight and heavy gasoline, are

somos takenoverhead. A light cycle stock or No. 2 fuel oil fraction is obtained as a sidestream and heav)l cycle stock as bottoms from atmospheric distillation unit 8. This p heavy cycle stock is returned as feed to the catalytic cracking unit or partly withdrawn as indicated in the drawing. v

The light cycle stock from distillation unit 8 is combined with the 10 to 50 percent bottoms from vacuum distillation unit 4, and the mixture is hydrodesulfurized and hydrocracked in unit 10. The hydrodesulfurized-hydrocracked product is then distilled in distillation unit 12 at atmospheric pressure. Desulfurized products such as gasoline, light gas-oil, etc., are removed as overhead and a desulfurized heavy gas-oil is removed from a lower section of the distillation unit. This desulfurized heavy gas-oil is combined with the heavy virgin gas-oil and catalytically cracked in unit 6 or removed and blended into No. 6 fuel oil. Desulfurized bottoms are removed from the base of tower or distillation unit 12.

We have found that there are definite economic advantages in utilizing conditions of intermediate severity during the combined hydrodesulfurizing and hydrocracking operation. This is illustrated by the following data which were obtained by combined hydrodesulfurizationhydrocracking of a 10.7 API blend containing 71.2

percent Kuwait vacuum tower bottoms (17 vol. percent of crude) (5.8 API) and 28.8 percent catalytically cracked furnace oil (22.7 API) under severe, medium and mild conditions. The conditions of operation in these tests are given in Tables I and II` while the analysis and yields of the products obtained are given in Tables III, IV

and V. Cost analysis of these results shows that a relinery operating on the intermediate severity basis will have a pay-out period of approximately 5.5 years less than the 10 mild and 1.5 years less than the severe conditions. The

catalyst used in these tests was nickel oxide-tungsten oxide deposited on activated alumina stabilized with silica. This catalyst contained 3% nickel (present as oxide) and 9% tungsten (present as oxide).

25 il Approximate temperature 835 and pressure 1,000 p. s. i. g.

TABLE II Case N n I II III Charge 17% Kuwait FCO Fuel 71. 2-28. 8% Blend Blend Blend Blond Bottoms Oil Dist. Blend Run Conditions:

OPEN-fin Down- Down- Down- Downow 110W flow flow Ha Feed: MSCF/B- 20 16 9 9 Reactor Temperature- Temperature: F. (Avg.) 836 836 833 834 Inlet Temp., F. (Avg.) 815 814 812 814 Maximum Temp. "F 860 858 863 848 Temp. Gradien F 44 51 Pressure: P. s. i. e 1,000 1,000 1,000 1,000 LHSV: V./V.lHr 0 47 0.52 1.08 1 04 LTP: V./V.-- l 89 8 62 4.31 24 9 Balance, Wt. Percent on Oil Charge:

Total Liquid 87. 2 91. 9 90. 6 94. 9 Dry Gas 5.2 3.3 3.4 1.6 Sulfur Elimnnte 4. 7 3. 4 3. 5 2. 2 Carbon 3. 3 2. 2 2. 2 0. 3

Total 100. 4 100. 8 99. 7 99. 0

Liquid Product:

Yield, Vol. Percent of Charge.-. 100 9 101. 3 99 3 100 5 Inspection- Gravity, API 5. 8 22. 7 10. 7 32. 5 25. 2 24. 3 19. 0 Viscosity, SUV 2 10, 346 2 352 3 17 100 39. l 3 451 35. 5 49. 4 65 0 1.85 Pour Point, F., ASTM D 97 above 115 +25 Color, ASTM Union 2 5 4+ 8+D 8-l-D 8lD Sulfur, Braun-Shell, Percent 5 45 2 66 4.87 0.18 1.46 1 36 2 72 Water and Sediment, Percent, ASTM D 96 0 4 0.2 Carbon Residue, Conradson on 590 F. Bottoms, Percent, ASTM D 189 19 8 0.24 4 15 2 0.38 9 33 9.00 17 66 Bromine No 29.7 11.2 19 7 17.9 24 2 Olens, Percent by Vol., ASTM D 875 43. 5 15. 2 Aromatic Content, Percent by Vol., ASTM D 875 37.3 Distillatiou, ASTM D 158- Over Point, F 434 458 124 158 168 174 10% at, F- 497 31s 382 392 439 50% at, F 652 518 Percent at 39 0 0 13 13 8 Percent at 500 F 12 4 42 30 28 18 Percent at 590 F 73 24 65 52 47 36 Aniline Point, F 98.4 Hydrogen Consumption:

S. C. F./B 927 745 430 Wt. Percent oi Charge 5 -1. 4 -1.2 -0. 7

1 Corrected for loss. 2 SUS at 210 F. 8 SFS at 122 F. 4 C. R. on total. 5 Minus sign indicates hydrogen was consumed.

l Braun-Shell sulfur, Bomb sulfur.

T4311??? Qae I pjjpdgllct..

l From ash vaporization of 670 F. bottoms. 2 Calculated. l Lamp sulfur.

The intermediate severity conditions are obtained by utilizing a space velocity of between about 0.5 and 1.0 and a throughput of between about 9 and 4 in the pressure and temperature ranges disclosed herein.

'As indicated above we have found that a nickel oxidetungsten oxide catalyst has definite advantages in the process of our invention. To demonstrate the superiority of this catalyst tests were run comparing it with typical catalysts such as cobalt molybdate, nickel, nickel oxide l iected to ud catalytic cracking. The product was fractionated and a light cycle oil (distillation range 400- 650) was separated. This cycle oil was combined with the vacuum tower bottoms (boiling above 1030 F. and .comprising 17 percent of the crude) in an amount such as to form a mixture of 71 percent vacuum tower bottoms and 29 percent cycle oil. This mixture was then hydrodesulfurized-hydrocracked in a fixed bed reactor, and in the presence of thecatalysts described above. The operor tungsten oxide which are known to have high utility 1 ating conditions and the results are given in Table VI.

TABLE VI Catalyst Charge: Kuwait V. T. Btms. 71% Cobalt Nickel FCC Light Molyb- Oxide- Cycle Oil date Tungsten Oxide Operating Conditions:

Hydrogen Recycle, Cu. Ft./Bbl 9,320 10, 590 Reactor Temperature, F., Aveva e 831 833 Reactor Pressure: P. s. i. g.-.-- 1, 000 1,000 Space Velocity, VolJHrJVol.-- 1. 0 0.9 Throughput, VOL/Vol 4. 0 3.8

Balance, Percent by Wt. of Charge:

Total T quid 93. 2 91. 3 Dry GM 2. 8 4. 0 Sulfur Removed 2. 5 2. 5 Carbon on Catalyst 1. 7 2. 5

Total 100. 2 100. 3

Liquid Product:

Yield, Percent by Vol. of Charge 100.0 99. 0 Inspection- Gravity, API 10. 2 20. 4 22. 1 Viscosity, SUV, Sec., 100 F. 2 386 154 94. 5 Color, ASTM Union 8-l-D 8+D S-l-D Sulfur, B-S, Percent 4.83 2. 38 2.34 Distlllation, ASTM D 158- Over Point, 458 186 End Point, F., Percent at:

392 F.1 0 13 23 500 F. 4 27 34 590 24 43 46 at, F-- 536 35e 224 1 Corrected tor loss.

EXAMPLE 1 The two catalysts used in this example were both deposited upon H-42 alumina which is an activated alumina manufactured by the Aluminum Company of America and containing about 4 percent of silica. Both` catalysts contained l0 percent of the active hydrogenating component deposited upon the alumina carrier, the metals being present in a 1:1 mol ratio. Thus, in the case of nickel oxide-tungsten oxide, the two oxides were present in a 1:1 mol ratio and the total nickel and tungsten con-l tent bas'ed on the oxide was 10 percent. p

A Kuwait crude was distilled to separate a lighter component constituting light gas-oil and lower boiling coinponents. The bottoms from this atmospheric distillation was then subjected to distillation in the presence 'of steam under reduced pressure of about -50 mm. of'mercury and a temperature of about 750 F. The overhead con- It will be noted from this data that the nickel oxidetungsten oxide catalyst exhibited considerably greater hydrocracking activity as shown by the gravity of the product and the desulfurizing activity was slightly greater than that of the cobalt molybdate. It is also to be noted that the nickel oxide-tungsten oxide catalyst gave a much greater yield of gasoline and a bottoms product having a much lower viscosity.

EXAMPLE 2 In this example three catalysts were tested, one containing nickel, another nickel oxide-tungsten oxide and the third tungsten oxide to compare their activity in lysts tested were deposited upon H-42 alumina having the composition described in Example 1. The amount of active component in each catalyst was substantially the same in each of the tests. The conditions and results Stituting heavy gas-oil boiling at 670l030 F. was sub- 75 of these tests are given in Tables VII, VIII and IX.

TABLE Corst Charge: Krovgit 1151711716111V n-127WNiW 127 W on ,0 l Bottoms H=42' omi-42 Afm2 1 alumina alumina alumina Operating Conditions:

Hydrogen Recycle, Cu. Ft./Bb1 10,325 10, 251 10, 566 Reactor Temperature, F.-

Avemge 827 832 831 Outlet 840 855 846 Reactor Pressure: P. s. 1. g.. 1, 000 1,000 1, 000 Space Velocity, Vol./Hr./Vol-. 1.00 0. 98 .96 Throughput, VOL/Vol 3. 98 3. 90 3. 84 Balance, Percent by Wt. of Charge:

Total Liquid 92:6 93. 3 91. 1v Dry Gas ca. 3.0 3.4 5.0 Sulfur Removed 2. 6 3. 2 3. 1 Garhnn 2. 15 2. 10 3. 24

Total 100. 3 101. 9 101. 9

Liquid Product:

Yield, Percent by Vol. of Charge--. 100. 2 102. 68 102. 1 Inspection- Y Y Gr ).vty, API 15.0 26.0 29.9 32. 2 Viscosity, SU 6. 320 76. 65- 5l. 8 39. 9 Co or, rASTM Union... Sel-D, 8-I-D 8:1-1) 8+D Sulfur, Braun-ShellgPercent; V4. 13 1. 6 8 1.05 1.18 Water and Sediment,A PercentY c ASTM D 9' 0:5 0.55 0. 2,5 0.8 Carbon. Residue. Cradspn 011 690 Bottoms; Percent ASTM D 189 10. 95 4. 76 4. 78; 3.42 Brmine No.-ASTM 1)"11598.- 16.9 12.0 13.0

I Corrected for loss.

TABLE VIII Catalyst Clrge: Kuwait.. 129' W on 12% NIW Bottomsy '-42 on H-42l A lunlina Alumina Balance, Percent by Wt; of Charge;

Total Liquid 92.8 93.3 Dry Gn" n 5.0 3.4 Sulfur` Removed. 2. 4 3. 1 Carbon. 2. 41 2. 10

Total 102. 6 101. 9

Liquid Product:

Yield, Percent by Vol. of Charge 101. 1 102. 58 Inspection- Gravity, API. 15. 0 28. 4 29. 9 Viscosity, SUV, Sec., 100 E-- 632.0. 62.1 51.8. Color, ASTM Union 8|eDf 8 +D S-l-D. Sulfur, Braun-Shell, Percent-. 4:13' 1. 77 1. 05' WaterandSediment, Percent, ASTM D-Q. 0. 5 0.2 0.25 Carbon Residue, Conradson on 690 Bottoms, Percent ASTM D 189... 10195' 5.64 4. 78 BromlneNo. ASTM D.1859-. 16.7 12:0 Distillatlon, ASTMJ) 158:.,

Over Point; F.' 462K f Percenmtiaor 0.o, 21 22.1.. Percent at 500 F 0.0 30 82. Percentat 590 2. 4' 41 43." 1 0%at.F, 278 2881"? TABLE 1x Hydrodesulfurzaton of 17% Kuwait vacuum tower bottoms over nickel-tungsten and tungsten catalysts Average of Cycles Charge 1-9, 11-13,

Inclusive Inclusive Catalyst 12% Nickel-Tungsten on H-42 Operating Conditions:

Average Temperature, "F 835 835 Pressure: P. s. i. g.. 1, 000 1,000

Space Velocity, Vol./Hr./Vol 0.66 0. 63 Carbon Deposit, Percent by Wt. of Charge 5.08 5.32 Liquid Product Inspection:

Gravity, API 5. 8 23. 7 22.9

Sulfur, Braun-Shell, Percent-- 5. 48 2.07 2. 23

Average oi Cycles Charge 1-9, 11-13,

Inclusive Inclusive Catalyst 12% Tungsten on lil-42 Operating Conditions:

Average Temperature, "F 83 839 Pressure: P. s. i. Q 1, 000 1, 000

Space Velocity, Vol.[Hr./Vnl 0. 0.63 Carbon Deposit, Percent by Wt. of Charge 6.27 5. 59 Liquid Product Inspection:

Gravity, oAPI 5. 25. 22. 3

Sulfur, Braun-Shell, Percent 5. 48 2.22 2.89

Table VII shows the nickel oxide-tungsten oxide catalyst had greater desulfurizing activity than either the nickel or tungsten oxide separately. Also, it will be noted that the nickel oxide-tungsten oxide catalyst resulted in somewhat lower carbon deposition than either of the other catalysts. While the nickel oxide-tungsten oxide catalyst had considerably higher hydrocracking activity than nickel as shown as shown by the gravity of the product it was initially lower in this regard than tungsten oxide. However, this greater activity of tungsten oxide for hydrocracking is lost rather rapidly, while the activity of the nickel oxide-tungsten oxide catalyst is retained. This is illustrated in Table IX Where thirteen cycles were carried out, each cycle involving an oustream period followed by regeneration under identical conditions. It will be seen that the nickel oxide-tungsten oxide catalyst continued to have very high desulfurization and hydrocracking activity; whereas, the tungsten oxide catalyst had dropped substantially below the nickel oxide-tungsten oxide catalyst both in desulfurizing and hydrocracking power. The data in Table 1X, iirst column, were obtained by averaging the results of runs one through nine to obtain the activity of the catalyst during initial stages of its life and runs eleven through thirteen to obtain the activity of the catalyst after a longer period of use. It will also be noted that Table VIH shows that even in the initial cycles the tungsten oxide catalyst is inferior to the nickel oxide-tungsten oxide catalyst when compared on similar conversion levels. Thus, when both catalysts are used under conditions which give the same degree of conversion, the sulfur removed by the nickel oxide-tungsten oxide catalyst is substantially greater, the carbon deposition is considerably less, the total yield of product is higher and the gravity of the product is higher.

What we claim is:

1. The process of treating a crude petroleum which contains sulfur compounds to desulfurize and convert into catalytic cracking charge stock which comprises in combination subjecting the crude to distillation to separate a bottoms fraction constituting between about l0 and 50 percent of the crude, simultaneously desulfurizing and hydrocracking the l0 to 50 percent bottoms portion by contacting with hydrogen at a temperature between about 775 and 880 F., at a pressure between about 200 and 2000 p. s. i. g. while in the presence of a nickel oxidetungsten oxide catalyst, said contacting taking place under conditions which result in a degree of conversion selected from the group consisting of medium conversion and mild conversion, said conditions being selected from space velocities between about 0.5 and 1 and a contact time of between about 4 hours and 24 hours.

2. The process for substantially converting an approximately l0 to 50 percent bottoms fraction of a crude petroleum into a catalytic cracking charge stock and for simultaneously desulfurizing said bottoms fraction which comprises contacting said bottoms fraction with hydrogen at a temperature between about 775 and 880 F., at a pressureV between about 200 and 2000 p. s. i. g. while in the presence of a nickel, oxide-tungsten oxide catalyst, said contacting taking place under conditions which result in substantial conversion into catalytic cracking charge stock, said conversion conditions being a space velocity between about 0.5 and 1 and a contact time of between about 4 hours and 16 hours, terminating the contacting, subjecting the catalyst upon which coke is deposited to combustion regeneration to remove coke therefrom and re-using the regenerated catalyst in said hydrogen treatment of said bottoms fraction.

3. The process of treating a crude petroleum which contains sulfur compounds which comprises in combination subjecting the crude to distillation to separate a gasoil fraction boiling between about 670 and 1030 F. and a bottoms fraction constituting between about 10 and 50 percent of the crude, subjecting the gas-oil fraction to catalytic cracking, fractionating the products from the catalytic cracking operation to separate a cycle stock boiling between about 400 F. and 670 F., simultaneously desulfurizing and hydrocracking a mixture of the bottoms fraction and the cycle stock by contacting with hydrogen at a temperature between about 775 and 880 F., at a pressure between about 200 and 2000 p. s. i. g. while in the presence of a nickel oxide-tungsten oxide catalyst, said contacting taking place under conditions which result in substantial conversion into catalytic cracking charge stock, said conversion conditions being a space velocity between about 0.5 and l and a contact time between about 4 and 24 hours, continuing said operation until suiiicient coke has been deposited on the catalyst to require regeneration, terminating the contacting, sub` jecting the catalyst upon which coke is deposited to combustion regeneration to remove coke therefrom and reusing the regenerated catalyst in the hydrogen treatment of additional mixture of bottoms fraction and cycle stock.

4. The process of treating a crude petroleum which contains sulfur compounds which comprises in combination subjecting the crude to distillation to separate a gasoil fraction boiling between about 670 and 1030 F. and a bottoms fraction constituting between about 10 and 50 1-5 percent of the crude, subjecting the gas-oil fraction to catalytic cracking, fractionating the products from the catalytic cracking operation to separate a cycle stock boil;

contacting taking place under conditions which result inv substantial conversion into catalytic cracking charge stock, said conversion conditions being a space velocity between about 0.5 and 1 and a contact time between about 4 and 16 hours, fractionating the hydrodesulfurized'fhydro-A cracked product to separate a fraction boiling between' about 670 and 1030 F., adding this fraction t the above-mentioned gas-oil prior to catalytic cracking, terminating the contacting, subjecting the catalyst upon which coke is deposited to combustion regeneration to remove coke therefrom and re-using the regenerated catalyst in Ithe hydrogen treatment of additional mixture of bottoms fraction and cycle stock.

5. The process of treating a crude petroleum which` contains sulfur compounds which comprises in combina-l tion subjecting the crude to distillation to separate'a gasoil fraction boiling between about 670 and 1030 F. and a bottoms fraction constituting between about 10 and 50 percent of the crude, subjecting the gas-oil fraction to catalytic cracking, fractionating the products from the catalytic cracking operation to separate a cyclestockY boiling between about 400 F. and 670 F., simultaneous' ly desulfurizing and hydrocracking a mixture of the'botf tomsfraction and the cycle"` stock by contacting with hydrogen at a'temperature between about 775 and 880 F., at alpressure between about 200 and' 2000 p. s. i. g. While in the presencev of a nickel oxide-tungsten o xide catalyst which contains between 0.1:1 .0 and 2 .0:1.0 m01 ratio of nickel oxide to tungsten oxide depositedv upon alumina containing between land 4 percent silica, said contacting taking place under conditions which result in substantial conversion into catalytic cracking charge stock, said conversion `conditions being a space velocity between about 0.5 and 1 anda contact time between about 4 and 16 hours, continuing said operation until suthcient coke has been deposited on the catalyst to require regeneration, terminating the contacting, subjecting the catalyst upon which coke is deposited to combustion regeneration to remove coke therefrom, re-using the regenerated catalyst in the hydrogen treatment of additional mixture of bottoms fraction and cycle stock and repeating the contacting and regeneration steps.

6. AA process for hydrocracking a residual oil having a low A. P. I. gravity and obtained by distillation of a crude oil to a gas oil product which process comprises contacting f said residual oil with a catalyst consisting essentially of nickel oxide and tungsten oxide supported on `a porous carrier at a temperature between about 775 and 875 F., at aA pressure between about 200 and 2000 p. s. i.Y g. and in the presence of added hydrogen in the amount between about 500 and 20,000 S. C. F./B.

7. A process for hydrocracking a residual oil to a gas oil product, said residual oil containing a substantial amount of residual components and having a low gravity which process comprises contacting said residual oil with a catalyst consisting essentially of nickel oxide and tungsten oxide supported on alumina at a temperature between about 775 and 875 F., at a pressure between i about 200 and 2000 p. s. i. g., at a space velocity between about 0.3 and 2 for a throughput of 4 to 24 and in the presence of added hydrogen in the amount between about 500 an`cl--20.000 S. C. F./B.

References Cited in the le of this patent UNITED STATES PATENTS 2,258,111 Engel Oct. 7, 1941 2,366,490 Cloud Jan. 2, 1945 2,486,361 Nahin et al. Oct. 25, 1949 2,500,146 Fleck et al Mar. 14, 1950 2,508,014 Davidson May 16, 1950 2,516,877 Home et al Aug. 1, 1950 2,548,015 Goodson et al Apr. 10, 1951 2,559,285' Douce July 3, 1951 2,642,381 Dickinson June 16, 1953 2,700,014 Anhorn et al. Jan. 18, 1955 2,700,015 Joyce Ian. 18, 1955 2,703,789 McKinley et al Mar. 8, 1955 

1. THE PROCESS FOR SUBSTANTIALLY CONVERTING AN APPROXIMATELY 10 TO 50 PERCENT BOTTOMS FRACTION OF A CRUDE PETROLEUM INTO A CATALYTIC CRACKING CHARGE STOCK AND FOR SIMULTANEOUSLY DESULFURIZING SAID BOTTOMS FRACTION WHICH COMPRISES CONTACTING SAID BOTTOMS FRACTION WITH HYDROGEN AT A TEMPERATURE BETWEEN ABOUT 775* AND 880*F., AT A PRESSURE BETWEEN ABOUT 200 AND 2000 P. S. I. G. WHILE IN THE PRESENCE OF A NICKEL OXIDE-TUNGSTEN OXIDE CATALYST, SAID CONTACTING TAKING PLACE UNDER CONDITIONS WHICH RESULT IN SUBSTANTIAL CONVERSION INTO CATALYTIC CRACKING CHARGE STOCK, SAID CONVERSION CONDITIONS BEING A SPACE VELOCITY BETWEEN ABOUT 0.5 AND 1 AND A CONTACT TIME OF BETWEEN ABOUT 4 HOURS AND 16 HOURS, TERMINATING THE CONTACTING, SUBJECTING THE CATALYST UPON WHICH COKE IS DEPOSITED TO COMBUSTION REGENERATION TO REMOVE COKE THEREFROM AND RE-USING THE REGENERATED CATALYST IN SAID HYDROGEN TREATMENT OF SAID BOTTOMS FRACTION. 